CN100446309C - Preparation method for controlling grain size of cathode material of tin - copper - nickel - cobalt alloy - Google Patents
Preparation method for controlling grain size of cathode material of tin - copper - nickel - cobalt alloy Download PDFInfo
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- CN100446309C CN100446309C CNB200710008998XA CN200710008998A CN100446309C CN 100446309 C CN100446309 C CN 100446309C CN B200710008998X A CNB200710008998X A CN B200710008998XA CN 200710008998 A CN200710008998 A CN 200710008998A CN 100446309 C CN100446309 C CN 100446309C
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Abstract
The preparation method includes two plating steps, and then procedure for sintering copper film. Plating solution 1 includes NiCl2 50-260g,CoCl2 8- 100g,H3BO3 2-40g,and distilled water 800-900mL. Plating solution 2 includes Na2SnO3.3H2O 30-95g,NaOH 10-100g,CH3COONa 10-50g,distilled water 800-900mL. Waveform of asymmetric current can be asymmetrical square wave, triangular wave, sine wave, impulse plating, sawtooth wave or combination of above waveform. After plating, cathode material is placed into tube furnace under condition of inert gas added, heating to 100-380 deg.C and preserving heat for 24h. After natural cooling, cathode material of tin cunico alloy is obtained. Features are: discharge capacity higher than 400mAh/g active matter, good cycle performance, and first time irreversible capacity lower than 15%.
Description
Technical field
The present invention relates to the preparation method of the asymmetric Current Control tin-copper-nickel-cobalt alloy cathode material of a kind of usefulness grain diameter.Utilize the alloy anode of this method preparation to can be applicable to field of batteries, particularly be applied to film-type lithium ion battery field.
Technical background
A large amount of mobile electronic devices, as mobile phone, camera and notebook computer etc. popularizing fast, have driven the lithium ion battery fast development all over the world.In recent years, the fast development of microelectronic component miniaturization has more urgent requirement to the exploitation and the film-type lithium ion battery of its coupling.Yet, the chemical property of existing electrode material and the requirement that preparation technology is difficult to satisfy film lithium ion battery.In order to address this problem, a large amount of research work have been carried out.Wherein, the preparation of the selection of novel negative material and new electrode is important research contents.
Sn and Li form Li
22Sn
5The theoretical specific capacity height of type alloy.But the cubical expansivity that forms this alloy very high (can reach 358%) is added intermetallic phase Li
xSn is very crisp, and cycle performance is bad.So, suit in Sn, to add nonactive, softer metal M [Pu W., He X., Ren J., et al.Electrochim Acta, 2005,50 (20): 4140-4145] from suppressing the angle of change in volume.Make metal M and Sn form the SnM alloy.When lithium in this SnM, embed, when deviating from, the ductility of M can make the cubical expansivity of Sn negative pole reduce greatly.At present, SnSb[Yang J., Takeda Y., Li Q., et al.J.Power Sources, 2000,90 (1): 64-69], SnNi[Ke F., Huang L., JiangH., et al.Electrochem.Commun, 2007,9 (2): 228-232], SnCu[Ren J., He X., Wang L., et al.Electrochim.Acta, 2007,52 (7): 2447-2452] etc. negative material all was studied.Wherein, gun-metal is one of negative material that is expected most.Copper can additional conductive in this negative material, also can provide stable frame structure.
Electrodeposition process is a kind of technology [Minoru Inaba, Takeshi Uno andAkimasa Tasaka, J.Power Sources, 2005,146 (1-2): 473-4777] of preparation film.Prepare lithium ion cell electrode with this method, can not use conductive agent, binding agent, make electrode have bigger volume and capacity ratio and low cost.The adhesion of alloy material and the collector of preparation is better than traditional coating method preparation.[Yang J., Winter M., Besenhard J.O., Solid State Ionics, 1996,90 (1-4): 281-287 such as Yang; Yang J., Wachtler M., Winter M., et al.Electrochem.﹠amp; Solid State Lett, 1999,2 (4): 161-163.] prepared the SnSb alloy material of different-grain diameter respectively with electrochemical deposition and chemical reduction method.Experimental result shows, has heterogeneous structure in SnSb.In their scope of experiment, sample particle is more little, and cycle performance is good more.When sample particle particle diameter during less than 300nm, the capacity of 200 circulation back samples can also reach 360mAh/g.The SANYO GS electric corporation has prepared a kind of SnCu membrane electrode [Tamura N., Ohahita R., Fujimoto M., et al.J.Power Sources, 2002,107:48-55].By electro-deposition, on the copper matrix, form the Sn thin layer, this film at 200 ℃ of annealing 24h, can be improved the adhesion of tin layer and base material, discharge and recharge 10 circulation back reversible capacities and still reach 800mAh/g.They find that annealing in process makes and form two kinds of different SnCu intermetallic compounds between tin layer and copper current collector layers.This copper has improved action intensity between active material and the collector in the concentration gradient of tin layer, has improved electrode performance.But, defectives such as pin hole and thick crackle appear in coating surface easily that prepare with the dc electrodeposition technology, have limited range of application.As the method for preparing electrode, may influence electrically contacting of active layer and collector.Asymmetric in recent years current technique is at the clear superiority that improves aspects such as quality of coating, performance and economical with materials, domestic and international numerous galvanizers author's attention [Jr S, Freire C, Ballester M.Surface and Coatings Technology have been caused, 1999,122:10; Ueda M, Dietz H, Anders A, et al.Electrochim Acta, 2002,48:377; TrdeauM, Nanostructured Materials, 1999,12:55].The coating that obtains with asymmetric current technique has strong adhesion, advantage [Chen Guohuas such as impurity content is low, coating is even, stable components, technology is simple, internal stress is low, ductility is good, Wang Guangxin etc. write, and electrochemical method is used, chemical industry publishing house, 2004, Beijing].In addition, because the charge and discharge process of tin-copper alloy cathode is typical solid liquid interface course of reaction, when the solid liquid interface performance is changed, as, sample particle particle diameter and particle are at the stability of charge and discharge process, sample surfaces polarity, sample surfaces hole etc., the rate controlled factor that discharges and recharges course of reaction may change, thereby changes polarization of electrode performance and the stability that discharges and recharges reaction when discharging and recharging.
Studies show that although through many improvement effort, tin base cathode material still manifests the larger volume expansion rate in the charge and discharge cycles process, capacity attenuation is bigger.For improving the cycle performance of kamash alloy, the present invention has adopted a kind of asymmetric electric current control method, and preparation is the tin-copper-nickel-cobalt alloy cathode material of the controlled grain diameter of matrix with copper.
Summary of the invention
The preparation method who the purpose of this invention is to provide the asymmetric Current Control tin-copper-nickel-cobalt alloy cathode material of a kind of usefulness grain diameter.
For realizing that the technical scheme that purpose of the present invention adopts is: copper film as negative electrode, after electroplate liquid 1 and 2 liang of step plating of electroplate liquid, is carried out solid-phase sintering.Specifically implement by the following technical programs.
1, the proportioning of electroplate liquid 1 (w/v)
NiCl
2 50-260g
CoCl
2 8-100g
H
3BO
3 2-40g
Distilled water 800-900mL
2, the proportioning of electroplate liquid 2 (w/v)
Na
2SnO
3·3H
2O 30-95g
NaOH 10-100g
CH
3COONa 10-50g
Distilled water 800-900mL
3, electroplating process
Copper film is put into the electroplate liquid 1 of temperature the 20-70 ℃ of arbitrary temperature in interval, the electric current that feeds asymmetric waveform in negative electrode is electroplated, the copper film that will coat nickel cobalt (alloy) is then put into the electroplate liquid 2 of temperature the 40-85 ℃ of arbitrary temperature in interval, electroplates in the electric current of negative electrode feeding asymmetric waveform equally.Perhaps copper film is put into electroplate liquid 2 earlier and electroplated, put into electric liquid 1 again and electroplate.After electroplating, two steps make tin Cu, Ni and Co copper matrix alloy.Electroplating time 0.2-38min.
4, sintering process
The tin Cu, Ni and Co copper matrix alloy of being electroplated preparation two steps places tube furnace, feeding flow velocity is the pure inert gas of 5-500mL/min, be heated to arbitrary temperature of 100-380 ℃ of temperature range simultaneously with the heating rate of 1-30 ℃/min, insulation 24h, naturally cool to room temperature with furnace temperature then, make the controlled tin-copper-nickel-cobalt alloy cathode material of grain diameter.
The electric current of asymmetric waveform of the present invention is meant the combination of asymmetrical square wave, asymmetric triangular wave, asymmetric sine wave, pulse current ripple, asymmetric sawtooth waveforms or above waveform electric current.The duty ratio of asymmetric electric current is 1000: 1-1: in 1000 intervals.
The current density of asymmetric waveform electric current of the present invention is at 0.3-3A/dm
2Between.
Inert gas of the present invention is meant pure argon air-flow or pure nitrogen gas air-flow.
Compare with other inventive method, cost of material of the present invention is lower, and raw material sources are extensive, and preparation process is simple, and is consuming time few.This electrode material has outstanding discharge performance and charge and discharge cycles stability, and discharge capacity is up to 400mAh/ first
The active goods and materials of gMore than, cycle performance is good, is expected to be applied in lithium ion battery, lithium battery, polymer Li-ion battery, particularly film-type (as thickness at 0.1 ~ 1000 μ m) battery.
Embodiment
Below in conjunction with embodiment the present invention is further detailed.Embodiment further replenishes and explanation of the present invention, rather than the restriction to inventing.
Embodiment 1
1, two step electroplating processs
(1) first step: the composition of electroplate liquid 1: NiCl
250g, CoCl
2100g, H
3BO
32g, distilled water 900mL, temperature of electroplating solution are 20 ℃.
Copper sheet is placed electroplate liquid 1, at average 0.3A/dm
2Pulse current under, electroplated 38 minutes in negative electrode, duty ratio is 1000: 1 during plating, obtains coating the copper sheet of nickel cobalt (alloy) rete.
(2) second steps: the composition of electroplate liquid 2: Na
2SnO
33H
2O 30g, NaOH 10g, CH
3COONa 10g, distilled water 800mL, temperature of electroplating solution are 40 ℃.
The copper sheet that coats the nickel cobalt (alloy) rete is placed electroplate liquid 2, at average 0.3A/dm
2Pulse current under, electroplated 38 minutes in negative electrode, duty ratio is 1000: 1 during plating, makes tin-copper-nickel-cobalt alloy.
2, solid-phase sintering process
The tin-copper-nickel-cobalt alloy of preparation is placed tube furnace, in the straight argon air-flow of flow velocity 5mL/min, be heated to 100 ℃ with the heating rate of 1 ℃/min, insulation 24h naturally cools to room temperature with furnace temperature, makes tin-copper-nickel-cobalt alloy cathode material.
Embodiment 2
1, two step electroplating processs
(1) first step: the composition of electroplate liquid 1: NiCl
2260g, CoCl
28g, H
3BO
310g, distilled water 900mL, temperature of electroplating solution are 40 ℃.
Copper sheet is placed electroplate liquid 1, at 0.5A/dm
2Cathode current under, electroplated 5 minutes with the asymmetrical square wave electric current, duty ratio is 100: 1, obtains coating the copper sheet of nickel cobalt (alloy) rete.
(2) second steps: the composition of electroplate liquid 2: Na
2SnO
33H
2O 30g, NaOH 30g, CH
3COONa 20g, distilled water 900mL, temperature of electroplating solution are 60 ℃.
The copper sheet that coats the nickel cobalt (alloy) rete is placed electroplate liquid 2, at 2A/dm
2Cathode current under, electroplated 38 minutes with the asymmetrical square wave electric current, duty ratio is 10: 3, obtains tin-copper-nickel-cobalt alloy.
2, solid-phase sintering process
The tin-copper-nickel-cobalt alloy of preparation is placed tube furnace, in the purity nitrogen air-flow of flow velocity 100mL/min, be heated to 150 ℃ with the heating rate of 10 ℃/min, insulation 24h naturally cools to room temperature with furnace temperature, makes tin-copper-nickel-cobalt alloy cathode material.
Embodiment 3
1, two step electroplating processs
(1) first step: the composition of electroplate liquid 1: NiCl
2150g, CoCl
250g, H
3BO
340g, distilled water 800mL, temperature of electroplating solution are 70 ℃.
Copper sheet is placed electroplate liquid 1, at average 1.5A/dm
2Cathode current under, electroplated 0.2 minute with asymmetric triangular current, duty ratio is 1: 10, obtains coating the copper sheet of nickel cobalt (alloy) rete.
(2) second steps: the composition of electroplate liquid 2: Na
2SnO
33H
2O 60g, NaOH 10g, CH
3COONa 50g, distilled water 800mL, temperature of electroplating solution are 60 ℃.
The copper sheet that coats the nickel cobalt (alloy) rete is placed electroplate liquid 2, at average 0.1A/dm
2Cathode current under, electroplated 15 minutes with asymmetric triangular wave, duty ratio is 10: 1, obtains tin-copper-nickel-cobalt alloy.
2, solid-phase sintering process
The tin-copper-nickel-cobalt alloy of preparation is placed tube furnace, in the purity nitrogen air-flow of flow velocity 200mL/min, be heated to 380 ℃ with the heating rate of 30 ℃/min, insulation 24h naturally cools to room temperature with furnace temperature, makes tin-copper-nickel-cobalt alloy cathode material.
Embodiment 4
1, two step electroplating processs
(1) first step: the composition of electroplate liquid 1: NiCl
2260g, CoCl
2100g, H
3BO
340g, distilled water 800mL, temperature of electroplating solution are 70 ℃.
Copper sheet is placed electroplate liquid 1, at 3A/dm
2Cathode current under, electroplated 3 minutes with asymmetric triangular current, duty ratio is 1: 100, obtains coating the copper sheet of nickel cobalt (alloy) rete.
(2) second steps: the composition of electroplate liquid 2: Na
2SnO
33H
2O 95g, NaOH 100g, CH
3COONa 50g, distilled water 900mL, temperature of electroplating solution are 85 ℃.
The copper sheet that coats the nickel cobalt (alloy) rete is placed electroplate liquid 2, at average 0.5A/dm
2Cathode-current density under, electroplated 20 minutes with asymmetric triangular current, duty ratio is 1: 1, obtains tin-copper-nickel-cobalt alloy.
2, solid-phase sintering process
The tin-copper-nickel-cobalt alloy of preparation is placed tube furnace, in the purity nitrogen air-flow of flow velocity 300mL/min, be heated to 300 ℃ with the heating rate of 30 ℃/min, insulation 24h naturally cools to room temperature with furnace temperature, makes tin-copper-nickel-cobalt alloy cathode material.
Embodiment 5
1, two step electroplating processs
(1) first step: the composition of electroplate liquid 2: Na
2SnO
33H
2O 50g, NaOH 10g, CH
3COONa 30g, distilled water 900mL, temperature of electroplating solution are 60 ℃.
Copper sheet is placed electroplate liquid 2, at average 1A/dm
2Cathode current under, electroplated 20 minutes with asymmetric sine-wave current, duty ratio is 100: 1, makes the copper sheet that coats the tin film.
(2) second steps: the composition of electroplate liquid 1: NiCl
250g, CoCl
250g, H
3BO
320g, distilled water 800mL, temperature of electroplating solution are 60 ℃.
The copper sheet that coats the tin film is placed electroplate liquid 1, at average 1A/dm
2Cathode current under, electroplated 10 minutes with asymmetric sawtooth current, duty ratio is 1: 1, makes to obtain tin-copper-nickel-cobalt alloy.
2, solid-phase sintering process
The tin-copper-nickel-cobalt alloy of preparation is placed tube furnace, in the purity nitrogen air-flow of flow velocity 500mL/min, be heated to 380 ℃ with the heating rate of 30 ℃/min, insulation 24h naturally cools to room temperature with furnace temperature, makes tin-copper-nickel-cobalt alloy cathode material.
Claims (6)
1. with the preparation method of the tin-copper-nickel-cobalt alloy cathode material of the Current Control grain diameter of asymmetric waveform, it is characterized in that the copper film negative electrode after electroplate liquid 1 and 2 liang of steps of electroplate liquid electroplate, carries out solid-phase sintering:
(1) proportioning of electroplate liquid 1
NiCl
250-260g, CoCl
28-100g, H
3BO
32-40g, distilled water 800-900mL;
(2) proportioning of electroplate liquid 2
Na
2SnO
33H
2O 30-95g, NaOH 10-100g, CH
3COONa 10-50g, distilled water 800-900mL;
(3) electroplating process
Copper film is put into electroplate liquid 1, feed the electric current of asymmetric waveform, copper film is electroplated as negative electrode, the copper film that will coat nickel cobalt (alloy) is then put into electroplate liquid 2, feeds the electric current of asymmetric waveform, electroplates in negative electrode; Perhaps the electric current of copper film being put into electroplate liquid 2 usefulness asymmetric waveforms is earlier electroplated, and puts into the electric current of electroplate liquid 1 usefulness asymmetric waveform again and electroplates, and prepares tin-copper-nickel-cobalt alloy;
(4) sintering process
To electroplate the tin-copper-nickel-cobalt alloy for preparing through two steps and place tube furnace, feed inert gas, the programming rate with 1-30 ℃/min is heated to predetermined sintering temperature simultaneously, insulation 24h, be cooled to room temperature, make the tin-copper-nickel-cobalt alloy cathode material of controlled grain diameter.
2, the preparation method of the tin-copper-nickel-cobalt alloy cathode material of the Current Control grain diameter of usefulness asymmetric waveform according to claim 1, the waveform that it is characterized in that the electric current of described asymmetric waveform is asymmetrical square wave, asymmetric triangular wave, asymmetric sine wave, pulse current ripple, asymmetric sawtooth waveforms or the combination of above waveform.
3, the preparation method of the tin-copper-nickel-cobalt alloy cathode material of the Current Control grain diameter of usefulness asymmetric waveform according to claim 1, the current density of the electric current of the asymmetric waveform that feeds when it is characterized in that electroplating is at 0.3-3A/dm
2Arbitrary value in interval, the duty ratio of current waveform is 1000: 1-1: 1000 interval interior arbitrary ratios, the arbitrary value of electroplating time in the 0.2-38min interval.
4, the preparation method of the tin-copper-nickel-cobalt alloy cathode material of the Current Control grain diameter of usefulness asymmetric waveform according to claim 1, the temperature that it is characterized in that electroplate liquid 1 is the arbitrary temperature in 20-70 ℃ of interval, and the temperature of electroplate liquid 2 is the arbitrary temperature in the 40-85 ℃ of interval.
5, the preparation method of the tin-copper-nickel-cobalt alloy cathode material of the Current Control grain diameter of usefulness asymmetric waveform according to claim 1, it is characterized in that inert gas used in sintering process is straight argon air-flow or purity nitrogen air-flow, the arbitrary flow velocity of flow velocity in the 5-500mL/min interval.
6, the preparation method of the tin-copper-nickel-cobalt alloy cathode material of the Current Control grain diameter of usefulness asymmetric waveform according to claim 1 is characterized in that sintering temperature is the arbitrary temperature in 100-380 ℃ of interval.
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Cited By (1)
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|---|---|---|---|---|
| US10892206B2 (en) | 2019-01-17 | 2021-01-12 | Toyota Motor Engineering & Manufacturing North America, Inc. | Methods of forming power electronic assemblies using metal inverse opal structures and encapsulated-polymer spheres |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108923024B (en) * | 2018-06-08 | 2020-10-23 | 浙江工业大学 | Magnetic lithium metal battery copper-magnetic composite electrode material, and preparation process and application thereof |
| CN111092216B (en) * | 2019-12-31 | 2021-03-16 | 河北科技大学 | Preparation method of nanowire type Sn-Ni alloy negative electrode material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1505188A (en) * | 2002-11-30 | 2004-06-16 | 中南大学 | Composite nano metallic negative electrode material for lithium ion battery and method for making same |
| CN1585160A (en) * | 2004-06-03 | 2005-02-23 | 清华大学 | Preparing method for negative material of high-capacity tin-base lithium ion battery |
| CN1738077A (en) * | 2005-09-06 | 2006-02-22 | 天津力神电池股份有限公司 | Method for preparing negative pole material of lithium ion cell high-capacity tin composite |
| CN1770512A (en) * | 2004-09-30 | 2006-05-10 | 索尼株式会社 | Anode active material and battery using it |
| US20070059598A1 (en) * | 2005-09-09 | 2007-03-15 | Aquire Energy Co., Ltd. | Cathode material for manufacturing a rechargeable battery |
-
2007
- 2007-05-23 CN CNB200710008998XA patent/CN100446309C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1505188A (en) * | 2002-11-30 | 2004-06-16 | 中南大学 | Composite nano metallic negative electrode material for lithium ion battery and method for making same |
| CN1585160A (en) * | 2004-06-03 | 2005-02-23 | 清华大学 | Preparing method for negative material of high-capacity tin-base lithium ion battery |
| CN1770512A (en) * | 2004-09-30 | 2006-05-10 | 索尼株式会社 | Anode active material and battery using it |
| CN1738077A (en) * | 2005-09-06 | 2006-02-22 | 天津力神电池股份有限公司 | Method for preparing negative pole material of lithium ion cell high-capacity tin composite |
| US20070059598A1 (en) * | 2005-09-09 | 2007-03-15 | Aquire Energy Co., Ltd. | Cathode material for manufacturing a rechargeable battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10892206B2 (en) | 2019-01-17 | 2021-01-12 | Toyota Motor Engineering & Manufacturing North America, Inc. | Methods of forming power electronic assemblies using metal inverse opal structures and encapsulated-polymer spheres |
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| CN101093885A (en) | 2007-12-26 |
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Assignee: Fuzhou Fran M & E Technology Development CO., Ltd. Assignor: Fujian Normal University Contract fulfillment period: 2008.12.30 to 2013.12.29 contract change Contract record no.: 2009350000002 Denomination of invention: Preparation method for controlling grain size of cathode material of tin - copper - nickel - cobalt alloy Granted publication date: 20081224 License type: Exclusive license Record date: 2009.2.9 |
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